Method of refining hydrocarbons



Patented June 24, 1930 UNITED sr-Aras' PATENT I oFmcEf JOHN J'OHNSTON, JB., OF ESGONDIDO, CALIFORNIA, ASSIGNOB OF ONE-HALF TO JAMES B. TOWNSEND, 0! LOS ANGELES, CALIFORNIA.

METHOD REFINING HYDBOCARBON S Re Drawing. Application filed August 11, 1925, Serial No. 49,648. Renewed March 28, 1929.

An object of this invention is to provide a simple, quick and economical method of producing refined petroleums such as gasoline, kerosene, lubricating oil, distillate and other cuts of petroleum from crude petroleum, shale oil and the like.

An object is to dispense with the expensive methods heretofore employed.

A further object is to produce a pure hydrocarbon product from crude petroleum.

An object is to produce from crude petroleum of an asphaltic base, a pure waterwhite petroleum product, which is not subject to change by the action of sunlight.

An object is to provide a sulphuric acid treatment of oil in which a minimum amount of sulphuric acid is used.

An object is to refine lubricating oils quicker and more cheaply than heretofore, and to produce from poor rades of hydrocarbon oils, and from crac ed oilsa lubri-' eating oil that is freer from corrosives than lubricating oils heretofore produced from such oor oils.

This application is a continuation-in-part of the ap lication filed b me March 28, 1923, entitled lethod' of refilling hydrocarbons, Serial No. 628,291.

Broadly considered the-discovery consists in distilling the hydrocarbon in the presence of a vehicle such as adsorbent clay or silicate of aluminum, charged with, and inert to sulphuric acid.

I have used the inert vehicle and acid in various proportions ranging from a mixture containing about 95 parts of said adsorbent clay and about 3 parts of sulphuric acid, to a mixture contaimng about 75 parts of said clay and about 25 parts of acid; the measurements being by Wei ht.

I have discovere that by distilling crude liquid hydrocarbon such as crude petroleum, shale oil and the like and the liquid products thereof in the resence of an acidulated finely powdered a orbent earth, com osed of silicate of aluminum 95-parts an sulphuric acid 3 parts the products coming ofi at the various customary temperatures, will be practically pure gasoline stock, kerosene stock, distillates, lubricating oil stock, and

other oils, without any further treatment except apossible redistilling in the same,

manner. 7

The acidulated adsorbent earth is in the form of a fine white earthy powder which shows acid reaction under litmus test, and is shown by analysis to be composed of silicate of aluminum, 95 parts; and sulphuric acid, 3 parts.

I do not limit the method to the use of the said acidulated adsorbent earth in the quantitative proportions above recited, but propose to employ any of the known equivalents constituting a vehicle for, and inert to, the sulphuric acid, with or without an added acid factor, as may prove most eflicacious.

The principle of the discovery or invention as at present understood b me, is the distilling and retorting of the oil under temperatures from the critical or boiling point of the oil up to the coking temperature of say about 750 degrees Fahrenheit, more or less, in the presence of a finely powdered adsorbent earth charged with sulphuric .ed. I may then redistill the various cuts separately in the presence of new charges of the acidulated adsorbent earth to produce the various final products above referred to. The distillation and redistillation effected in the present of the acidulated adsorbent earth may be repeated as often as desired.

The amount of highly adsorbent, finely divided, acidulated porous earth required may vary and I have found that satisfactory results may be obtained by the use of such acidulated adsorbent earth in the proportion of from 2 parts to 10 parts of the earth to 100 parts of the shale oil or crude petroleum; the proportion varying according to the character of the oil and the amount of impurities therein.

In practice I thoroughly mix the said finely powdered acidulated adsorbent earth with the oil to be treated and subject the mixture to the requisite temperature or temperatures in the appropriate apparatus, as a still or retort such as is common in the art of distilling or retorting oil; and I take off the various cuts in the usual way and at the usual temperatures until all that is left is,

the predetermined residuum which may be a liquid, a semi-liquid, a gum or a solid.

The respective cuts may be separately redistilled with fresh charges of the above described acidulated earth or its equivalent mixed in the oil contents of the still.

The products obtained by the method above set forth are clearer and purer than the commercial products with which I am familiar and retain their water-white color in the presence of sunlight.

As one method of illustrating my process, I took a very dirty, bad smelling oil obtained from the surface sands of San Luis Obispo County, California, and recovered by flotation. This particular type of oil distilled in the ordinar manner commonly in use everywhere, pro need a dirty, dark colored evil smelling reddish gasoline, kerosene and lubricating stock, all of it more or less filled with sediment, and after a few da s standing in light, it colored, became dar ened and reddened and the odor became very offensive.

I took about 1500 cubic centimeters of this oil and put it in a copper still with about 100 cubic centimeters of adsorbent clay acidulated with sulphuric acid.

I then heated the still and its contained mixture of acidulated absorbent clay and oil by a gas flame until the initial boiling point of about 120 F. was arrived at and the gasoline stock and the kerosene stock came over water-white, and have remained so for a period of over four years.

The lubricating oils were of proper colors, clear and also remained so. Practically all of the odor was one. About 87% oil was distilled at 600 the gasoline content in this particular sample was about 20%, kerosene about 16%, balance being light, medium and heavy lubricating oils and asphaltum. Lubricating oils were of a good quality, with none of the characteristic red color, and only a slightly disagreeable odor which can easily be removed by distillation process. As this was an' asphaltum oil there was no wax.

I have thus demonstrated that by this novel method I have been able to treat crude and cracked hydrocarbon oils with only three-tenths of one part of sulfuric acid, and

with results superior to those heretofore known; and that like superior results may be secured by the same method in treating the different cuts; and that the lubricants thus produced will not contain the corrosive element present in lubricating oils produced by former methods.

While there appears from analysis that the acidulated adsorbent earth I have used has a small content of water, my experiments indicate that the water is detrimental and that it is advisable that the inert powdered vehicle for the sulfuric acid be dehydrated to as full an extent as practical.

I claim:

1. The method set forth of refining liquid hydrocarbon which consists in producing a mixture of such liquid and acidulated adsorbent earth composed substantially of silicate of aluminum, 95 parts;

and sulphuric acid, 3 parts; heat treating the mixture to approximately 750 F., and liquefying the resulting vapors obtained during such heat treatment.

2. The method set forth .of refining liquid hydrocarbon which consists in making a mixture of such liquid and acidulated powdered porous earth, containing silicate of aluminum, about 95 parts; and sulphuric acid 3 parts, and converting the mass by heating the mass to a temperature in successive stages varying from about 120 to 750 F., to recover distinct and separate forms of commercial products as set forth.

3. The method set forth of refining liquid hydrocarbon which consists in thoroughly incorporating with the liquid a finely powdered acidulated adsorbent earth composed substantially of silicate of alumina, 95 parts, and sulphuric acid 3 parts, in the proportions substantially of from two to ten per cent in volume thereof to one hundred parts of the oil, converting the mass in successive stages by varying degrees of heat from 120 to 750 F., collecting the resultant vapor and by condensation, securing the commercial products set forth.

4. The method set forth of refining liquid hydrocarbons, which consists of making a mixture of acidulated adsorbent earth composed of silicate of aluminum'95 parts; and sulphuric acid 3 parts, converting the mass by applying .heat thereto, collecting the resultant vapors from the mixture and condensing the said vapors to specific cuts in accordance with the varying degrees of heat applied.

5. The method as substantially set forth of producing a refined petroleum product which method includes subjecting a mixture of petroleum and acidulated adsorbent earth composed of silicate of aluminum 95 parts; and sulphuric acid 3 parts, to heat in degrees of temperature varying from about 120 to 750 F., and at successive stages confinin the resultant vaporized produc, and y condensing the latter, eculrling the refined commercial product set ort 6. The method of producing purified petroleum products from crude petroleum oil, which consists substantially in mixing 100 parts of crude oil with from 2 to 10 parts of adsorbent clay or silicate of aluminum acidulated with sulphuric acid,

which clay substantially constitutes a vehicle inert to the acid and forms with the sulphuric acid a mixture in pro ortions varying from about 95 parts of sai clay to 3 parts of said acid, upto a mixture of parts of said clay to 25 parts of said acid;

said proportions being by weight; and distilling. off and thus recovering the hydrocarbons at the required heat substantially as set forth.

In testimonywhereof, I have hereunto set my hand at Escondido, California, this 21st day of July 1925.

.ioHN JOHNSTGN, JR. 

